JPH016A - plant growth regulator - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application: The present invention relates to a plant growth regulator, and more specifically, it is represented by the following general formula (1) [wherein R1 is hydrogen, lower alkyl, nitro, halogen, phenyl which may be substituted with one or more substituents selected from lower alkyl and lower alkoxy, R2 is hydrogen, halogen, lower alkoxy, lower alkylthio which may be substituted with lower alkoxycarbonyl, halogen or phenylthio optionally substituted with lower alkyl, phenylamino, phenylsulfonyl or heterocyclic thio optionally substituted with lower alkyl, X is oxy or the formula: N-Z (wherein Z is hydrogen; hydroxy or Lower alkyl optionally substituted with lower alkanoyloxy; phenyl optionally substituted with one or more substituents selected from carboxy, hydroxy, halogen, nitro, lower alkyl and lower alkoxy; phenoxy; F.

~1 means the number of double bonds] Contains one or more compounds as active ingredients, or contains one or more compounds and ethephon as active ingredients. The present invention relates to a plant growth regulator comprising:

Problems to be solved by the conventional technology and the invention: For example, ethephon has been used as a delamination accelerator to induce detachment of mature fruits, but it causes chemical damage (defoliation, harm to orchard visitors). In addition, there are problems such as the fact that it acts on immature fruits, and there is a desire for the development of new plant growth regulators that do not have or have fewer of these problems.

Means for Solving the Problems: In order to solve these problems, the inventors conducted extensive research and found that the compound represented by the general formula (1) causes chemical damage such as leaf fall and harm to garden visitors. We have obtained new findings that the compound shown by the general formula (I) does not act on immature fruits, acts only on mature fruits, and has an effect of promoting peel formation that promotes abscission of the fruits. The present invention was completed based on the discovery that a compound represented by formula (I) exhibits a synergistic effect when used in combination with ethephon, and that the compound represented by formula (I) also has a plant growth inhibiting effect (herbicidal activity).

The compound represented by the general formula (1) used as an active ingredient in the plant growth regulator of this invention includes new and known compounds, and the new compound can be prepared by a method similar to that described by Bunkei below or by a method described below. Manufactured by the method shown in the example.

Next, the definition of the compound represented by general formula (I) will be explained.

Unless otherwise specified, the term "1-lower" refers to a group having 1 to 6 carbon atoms.

The term "lower alkyl group" means a linear or branched saturated lower aliphatic hydrocarbon residue, and preferred examples include methyl, ethyl, propyl, isopropylAv, butyl, isobutyl, Examples include tertiary butyl, pentyl, hexyl, and the like.

The term "lower alkoxy group" means a group in which a linear or branched saturated lower aliphatic hydrocarbon residue is bonded to oxygen, and preferred examples of such groups include methoxy, ethoxy, propoxy, iso Examples include propoxy, butoxy, imbutquin, tertiary butoxy, pentyloxy, hexyloxy and the like.

"Halogens include fluorine, chlorine, bromine, and iodine.

The term "lower alkylthio group" means a group in which a linear or branched saturated lower aliphatic hydrocarbon residue is bonded to sulfur, and preferable examples of such groups include methylthio, ethylthio, propylthio, 'isopropylthio,
Examples include butylthio.

Preferred examples of 1-lower alkoxycarbonyl include:
Examples include methoxycarbonyl, ethoxycarbonylbonyl, imbutoxycarbonyl, tertiary butoxycarbonyl, and the like.

Preferred examples of ``1 heterocyclic thio'' include, for example, 5- to 6-membered unsaturated heterocyclic thio containing at least one nitrogen atom as a hetero atom (e.g., pyrazolinylthio, pyridylthio, pyrimidylthio, etc.); Examples include 5- to 6-membered unsaturated heterocyclic thio containing one nitrogen atom and one sulfur atom (eg, thiazolylthio, thiadiazolylthio, etc.).

Preferred examples of "lower alkanoyloxy" include acetoxy, propionyloxy, butyryloxy, isobutyryloxy, and the like.

Among the compounds represented by the general formula (I) used as active ingredients in the plant growth regulator of this invention, representative compounds are as follows (the compound numbers are shown in the table of test examples below). ).

29 8 HN) I 0
107115 P 10385 g 025 a 11358 g 77 So15f 798 f 13771 g 13771 g 340 e 23430 e 89129 d 54HHNHI Among the compounds represented by the general formula (I), production examples of representative examples of new compounds are shown below. Shown below.

Production Example 1 Thiophenol (1,70g) and 2-(3-chlorophenyl)maleimide (2,60g) in ethanol (so
mQ) Reflux the solution for 3.5 hours.

After distilling off the ethanol, the residue was recrystallized from ethanol:n-hexane to give 2-(3-chlorophenyl)-
3-phenylthiosuccinimide (1,10g) is obtained. mp 104-106℃LR(Nujol)'
3150.3050.1780.1695 cm-'N
MR(CDC13,S>' 3.88,4.05
(2H-ABq-J=6Hz).

7, OO~7.67 (9H, m), 8.58 (I
H, broad s) The following compound was obtained in the same manner as in Production Example 1.

Production Example 2 2-(2-chlorophenyl)-3-ethoxyluponylmethylthiosuccinimide mp 115 (18°C IR (
Nujol): 3130.3050.1760.1
730°1700 cab-1 NMR (CDC13,l; )' 1.26 (3H
9t, J=7Hz), 3.19°3.75 (2H, A
Bq, J=15Hz), 4.16 (2H,q.

J=7Hz>, 4.54. 4.94 (2H, A
Bq, J=9Hz).

7.17~7.50 (4H, m), 8°90 (
IH, broad s) Production Example 3 2-(2-chlorophenyl)-3-(2-pyridylthio)succinimide mp 15g-160°C IR (Nuj
ol): 3140.3040.1770.1695
crm-'NMR(DMSO-ds,l;)'
4.77.4.93 (2H1d, J=8Hz>.

7.0O~8.40 (8H, m), 11.83 (
IH, broad s) Production Example 4 2-(2-chlorophenyl)-3-phenylthiosuccinimide mp77-83°C IR (Nujol)' 3130.1780.169
5 am-1HMR (CDCl2.8)' 4.0
9,4.28 (2H, ABq, J=7Hz).

7, OO”7.67 (9H, m), 8.83 (I
H, broad s) Production Example 5 2-(2-chlorophenyl)-3-(4-chlorophenylthio)succinimide mp40-50°C NMR (CD
Cl2. δ): 4.12.4.25. (2H, AB
q, J=6Hz).

7, OO~7.57 (8H, m), 8.80
(LH, broad s) Production Example 6 2-(2-chlorophenyl)-3-(4-methylphenylthio)succinimide mp44-55°C NMR (CD
Cl2.8): 2.33 (3H, s), 4.4
6.4.91 (2H, ABq, J=6Hz), 6.9
7-7.50 (8H, m), 8.63 (LH, br
oad s) Production Example 7 2-(4-methylphenyl)-3-phenylthiosuccinimide mp 130-134°C LR (Nujol)
:3170.3060.1790.1700 cm-I
NMR (CDCl2.8)' 2.33 (3) 1
．． s), 3.88, 4.03 (2H, ABq, J=5H
z), 7.0-7.6 (9H, m), 8.73 (
IH, broad s) Production example 8 2-phenyl-3-phenylthiosuccinimide m
p109-112℃ IR (Nujol): 3175.3060.178
3.1700 am″″INMR(CDCl2. l;
): 3.91.4.08 (2H,ABq,J=
5Hz).

7.0-7.6 (10H, m), 8.66 <IH
, broad s) Production Example 9 2-(2-,jtoxyphenyl)-3-phenylthiosuccinimide 108-110°CIR (Nujol)
: 3150.3050.1778.1710 am
-INMR (CDCl2.δ): 3.90 (3H
,s), 3.91.4.14<28. ABq, J=5
Hz), 6.67=7.66 (9H, m), 8.
51 (IH, broad s) Production example 10 2-(4-methoxyphenyl)-3-phenylthiosuccinimide mp108-110°C IR (Nujol)
' 3160.3050.1775.1708 cm-
INMR (CDC13,8)' 3.80 (3H9
s), 3.91, 4.06 (2H, ABq, J-5) 1
z), 6.70-7.67 (9H, m), 8.6
0(IH, broad s) Production Example 11 2-(4-nitrophenyl)-3-phenylthiosuccinimide mp 142-145°C IR, (Nujol)
: 3190.3050.1785.1695 cm
-'NMR(DMSO-d6.δ): 4.30.
4.87 (2H, ABq.

J=8Hz>, 7.30~7.50 (5H, m),
7.57 (2H, d.

J-8Hz), 8.17 (28,d, J=8Hz)
, 11.78 (IH.

broad s) Production Example 12 2-(2-nitrophenyl)-3-phenylthiosuccinimide (oil) 1R(CDCl2): 3370.1780.171
5 am NMR (CDC13, δ): 4.11.4
．． 33 (2H, ABq, J near) 1z).

7.17"8.18 (9H, m), 8.57 (I
H, broad s) Production Example 13 A solution of the sodium salt of mercaptothiazoline (4,50&) in tetrahydrofuran (30 mQ) was refluxed with a solution of 2-(2-chlorophenyl)maleimi F (3,00 g) in tetrahydrofuran (40 mQ). reflux for 10 minutes. After cooling, the reaction solution is cooled with dilute hydrochloric acid, and the solvent is distilled off. The residue is extracted with ethyl acetate, washed with water and then dried over magnesium sulfate. After distilling off ethyl acetate,
The residue was subjected to silica gel chromatography and eluted with a mixture of dichloromethane and methanol (50:1). The eluate is recrystallized from ethanol to give 2-(2-chlorophenyl)-3-(2-thiazolin-2-ylthio)succinimide (1.40 g). mp 195-20
0℃.

IR (Nujol): 3150.1775.171
0 am-'NMR (DMSO-d6.δ): 3.
40 (2H, t, J=7Hz), 3.67-4.5
0 (2H, m), 4.93 (LH, d, J=8H
z>, 6.13 (IH, d, J=8)1z), 7.
17-7.67 (4H, m), Ll, 93 (LH,
Broad s) The following compound was obtained by a method similar to Production Example 13.

Production example 14 2-(2-chlorophenyl)-3-butylthiosuccinimide mp70-72°C IR (Neat): 3200.3050.1770
．． 1710 am-INMR (CDC13,8)'
0.67-1. OO (3R9m), 1-00~1.90
<41. m), 2.80 (2H, t, J: 6Hz
>, 3.88゜4.07 (2H, ABq, J:6H
z), 7.17-7.60 (4H, m).

8.87 (LH,m) Production Example 15 2-(2-chlorophenyl)-3-(5-methylthiadiazolyl-2-thio)succinimide mp 189-1
93℃ IR (Nujol): 3130.3030.178
8.1715 am-'NMR (DMSO-da, f;
)' 2.50 (3H,s), 4.97 (L
H9d.

7Hz>, 6.32 (IH, d, J=7Hz),
7.17=7.66 (4H, m) Production Example 16 2-(2-10 Lofenyl)-3-ethoxysuccinimide mp 175°C LR (Nujol): 3150.3050.179
0.1700 am-'NMR (CDCl2.δ):
1.17 (3H, t, J=8Hz), 3.3~4
．． 1 (2H, m), 4.20.4.60 (28,A
Bq, J=5Hz).

7.20~7.7 (4H, m), 8.70 (LH
, broad s) Production Example 17 2-(2-chlorophenyl)maleimide (4,70g)
and aniline (3,06 g) in ethanol (5011 m
) After concentrating the reaction mixture, reflux the solution for 38 h.
The residue was subjected to silica gel chromatography and eluted with a mixture of n-hexane and ethyl acetate (4:1 to 1:1).
2-(2-chlorophenyl)-3-anilinosuccinimide (oil) (3,71 g) is obtained.

IR(Neat) =3500-3000.1780.
1700 am-'NMR (CDCl2.8):
4.03.4.20 (2H, ABq, J=7Hz).

4.85 (1)1. broads), 6.3~7
．． 6 (9H, m), 8.96 (LH, broad
s) Production Example 18 N-(4-chlorophenyl)maleimi)' (6,23g
) and thiophenol (3.31 g) were refluxed for 1 hour. After cooling, the precipitate was collected by filtration and recrystallized from ethanol to obtain N-(4-chlorophenyl)-2-phenylthiosuccinimite (7.70 g). mp
153-155℃ IR (Nujol): 1690
am-1HMR (CDCl2.δ): 2.83
(LH, dd, J=4Hz, 19Hz).

3.35 (LH, dd, J: 8Hz, 19Hz),
4.15 (IH, dd.

J=4Hz, 8Hz), 7.03 (2H, d, J
=9Hz), 7.76-7.23 (7H, m) The following compound is obtained by a method similar to Production Example 18.

Production Example 19 N-(3,4-dichlorophenyl)-2-phe, nylthiosuccinimide mp 154-155.5°C IR
(Nujol): 1780.1690 am-1H
MR (CDCl2.δ): 2.86 (LH, dd
, J=4Hz, 18H2).

3.38 (IH, dd, J=8Hz, 18Hz),
4.15 (LH, ddJ=4Hz, 8)1z),
7.80-6.80 (8H, m) Production Example 2O N-(3-chlorophenyl)-2-phenylthiosuccinimide mp84-86°C IR (Nujol): 1780.1700 cm-
'NMR (CDC1a, 8)' 2.86 (LH
, dd, J=4Hz, 18Hz).

3.40 (LH, dd, J=8.5Hz, 18Hz
>, 4.18 (LH.

dd, J=4Hz, 8.5Hz), 7.90-6.
80 (9H, m) Production Example 21 Cyclohexylamine (59.4 g) is added to a solution of 2-(2-chlorophenyl)maleimi F anhydride (125.0 g) in acetic acid (1,21) and refluxed for 12 hours.

After distilling off the solvent, the residue was dissolved in ethyl acetate (500 mQ).
dissolve in The solution is washed successively with 5% hydrochloric acid (1501d), an aqueous sodium bicarbonate solution (500111fl) and water (150mQ), and then dried over magnesium sulfate. The solvent was distilled off and the residue was distilled to obtain N-cyclohexyl-(2-chlorophenyl)maleimide (oil) (90.2 g), bp 171-176
℃10.8on IR (Film): 1765.1700 cm-1
HMR (CDC1a, 8)' 0.8-2.6 (
IOH, m), 3.7-4.3 (LH, m), 6.
90 (IH, s), 7.15-7.90 (4H,
m) The compound represented by the general formula (I) has a specific plant growth regulating effect (e.g., promoting dehiscence formation in mature fruits).
For example, by spraying a drug containing the compound on mature fruit, it is possible to promote the formation of abscission layers on the fruit without damaging the leaves or fruit, and as a result, only the fruit is dropped or the fruit is not dropped. make it easier. Also, the compound does not affect immature fruit.

Therefore, by using the plant growth regulator of the present invention, it is possible to easily harvest fruits manually or mechanically.

Plants that can be applied for this purpose include fruit trees in general, but for example, by applying it to citrus fruits (e.g., oranges, kumquats, etc.), coffee, olives, koshiyo, nuts, etc., it is possible to specifically improve the effects of these fruits. Harvesting work can be made easier.

When applied to these plants, it is appropriate to spray 3 to 20 days, preferably 5 to 10 days before the fruit harvest time.

The compound represented by the above general formula (I) also has weed control activity, such as barnyard grass, crabgrass, foxtail grass,
It can be used to control weeds such as blackweed, chickweed, and sparrowweed.

Furthermore, when the compound represented by the general formula (1) is used in combination with ethephon [2CH2P(OH)2 on CIC], which has been conventionally used as a fruit delamination accelerator, the delamination effect on fruits is synergistic. Therefore, the compound represented by the general formula (I) can not only be used alone as a fruit delamination formation promoter, but also can be used in combination with ethephon. In the case of this combination, it is appropriate to use them in a proportion of about 1 to 1 part by weight per 100 parts by weight of the compound represented by the general formula (I).

The method of using the plant growth regulator of the present invention varies depending on the target plant, but it is generally appropriate to spray the plant growth regulator over the entire surface of the tree. The concentration used varies depending on the target plant, but is generally 1 to 5000 ppm, preferably 1
It is used in a range of about 0 to 11,000 pp.

When using the plant growth regulator of this invention, it is mixed with various carriers depending on the usage situation, such as powder, granules, tablets, etc.
It can be used as a wettable powder, emulsion, etc. The carrier mentioned here may be either solid or liquid, or a combination thereof.For example, talc, clay, kaolin, diatomaceous earth, calcium carbonate, potassium chlorate, saltpeter, nitrocellulose, starch, gum arabic, Water, alcoholic benzene, acetone, etc. are used as carriers. Furthermore, auxiliary agents used in the formulation of agricultural chemicals, such as spreading agents and emulsifiers, can be added as necessary.

Any of the preparations can be used not only alone, but also in combination with fungicides, insecticides, herbicides, other plant growth regulators, or fertilizers.

Effects of the invention: Next, the effects of the plant growth regulator of the invention will be explained using test examples.

Test Example 1 (Kumquat fruit withdrawal promoting effect) = 30 kumquat trees with fruit of varying size (extreme height: 40-50 cm)
One plant was planted in each pot with a diameter of 30 cm for trial use. During the fruit ripening period, an emulsion containing the plant growth regulator of the present invention (compounds listed in the table below) was prepared as in Example 1, and 500 p.
A diluted solution with water was prepared (7 samples) to give a concentration of pm. The spraying was done so that the entire surface of the tree was evenly wetted.

Two Niki trees were tested on each side, and after spraying the chemicals, they were placed in a glass room (
Room temperature: 12°C to 28°C). 5 days after spraying the chemical,
Twenty fruits were pulled from each tree by hand, and the state of fruit detachment was examined according to the following criteria. Based on the following criteria, the average withdrawal value for each drug was calculated from the withdrawal state of all fruits using the following formula. The results are shown in the table below.

Incidentally, no promotion of defoliation was observed by spraying the chemical of this invention.

Criteria for determining the detachment status of each fruit (difficulty in detachment) 1: Easy to pull off (separated without any damage to the peel or abscission part) 2: Slightly easy to pull off (with small scratches on the peel or abscission area) 3: Difficult to pull off (skin is severely damaged) Compound number Tamahime theory j 1 87.52
97.55
64.09 6
3.0” JI Lilo L Sanhiki member 11 12 51.513
82.514
92.515 g9.51
8 60.519
53.520
55,02g 63.031
77.535
67.536 70
,038 96,039
96, 541
86.042 85°5
44 79, 046
58.047
95, 554 81.0 Compound No. Average withdrawal value 55 78.0 No treatment 0 Test Example 2 (Investigation of withdrawal promotion effect and defoliation rate of kumquat fruits by combined use of ethephon and the plant growth regulator of the present invention): A test was conducted to examine the withdrawal promoting effect of kumquat fruit under the same conditions as Test Example 1, except that a combination of a plant growth regulator and ethephon was used. The spray solution was the emulsion diluted solution used in Test Example 1 with an ethephon concentration of 25 or 11.
00 pp. As ethephon, a commercially available agent (manufactured by Nissan Chemical Industries, Ltd., containing 10% component) was used.

At the same time, the rate of leaf fall was investigated and expressed as the ratio of the number of fallen leaves 10 days after spraying to the number of leaves at the time of spraying, and is shown in parentheses in the table below.

The results are shown in the table below.

this invention vinegar. ) Compound concentration 0 25 to.

Number (ppm) 0 0 (0,8> 10.5(1,3) 48
．． 0(6,8)1 300 54.0(0,9)
91.5 (1,6) 100 (8,0) 500
97.5 (0,9) 100 (1,5) 100
(8,2)0 0 (0,8>10.5(1,
3>48.0(6,8>14 30
0 47.0(0,8>94.0(1,4)
100 (7,2)500 93.0(1,
0) 100 (1,4) 100 (7,7)0
0 (0,8>10.5<1.3> 48.
0 (6,8) 38 300 55.0 (0,7)
96.0 (1,1>100 (7,7)500
96.0 (1,0) 100 (1,6>100
(6,9) Test Example 3 (Growth inhibitory effect by seed germination end treatment): A filter paper was placed on a 7 cm diameter yarn, and the plant growth regulator of this invention (compounds listed in the table below) was added to a predetermined amount of acetone o, smn. (dissolved) is added dropwise. After the acetone had evaporated, 5 tablespoons of water was added, and then 10 millet seeds each were placed on filter paper and allowed to germinate and grow at 25°C for 7 days. Illumination (40001ux) was hit in the lead race during this time. After 7 days, the fresh weight of the seedlings was examined, and the percentage of the untreated fresh weight was calculated. From this calculation result, the degree of growth inhibition was calculated based on the following criteria. The results are shown in the table below.

2: Same <26 to 50%, but less 51 to 75% 0: Same <76% or more Plant growth regulator of this invention Degree of growth inhibition (indicated by compound number) -1 study-1 test Example 4 Citrus cultivated in the field (variety: Hyuganatsu, C1tr)
The efficacy of the compounds of this invention was determined using mature trees of Tamurana Takahashi (Tamurana takahashi). An emulsion containing the following compound was prepared, diluted with water to a concentration of 500 ppm, and sprayed on every branch bearing 15 to 20 fruits during the fruit ripening stage. The spray was applied so that the fruits and branches and leaves were evenly wetted. Six days after the spraying, the fruits of each plant were hand-picked, and the effect of the drug was determined by the same method as in Test Example 1 based on the state of detachment of the delaminated part.

The results are as follows.

Compound number Kurebegai 1 83, 5 not sprayed
0 Next, examples of the present invention will be shown.

Example 1 (emulsion) 2-(4-chlorophenyl)-3-phenylthiosuccinimide 20 parts xylene 30 parts isophorone 30 parts Tulpol 90
48 Mix 20 parts 1- to make an emulsion.

Example 2 (Wettable powder) 2-(4-chlorophenyl)-3-phenylthiosuccinimide 20 parts Sodium ligninsulfonate 2 parts Polyoxyethylene alkyl ether 2 parts Dicrite
76 parts The above ingredients were mixed to prepare a wettable powder.

Patent applicant: Fujisawa Pharmaceutical Co., Ltd. Nissan Chemical Industries Co., Ltd.

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 is hydrogen, lower alkyl, or one or more substituents selected from nitro, halogen, lower alkyl, and lower alkoxy. R^2 is hydrogen, halogen, lower alkoxy, lower alkylthio optionally substituted with lower alkoxycarbonyl, phenylthio optionally substituted with halogen or lower alkyl, phenylamino, phenyl, which may be substituted with phenyl; a heterocyclic thio optionally substituted with sulfonyl or lower alkyl, X is oxy or the formula: N-Z (in the formula,
Z is hydrogen; lower alkyl which may be substituted with hydroxy or lower alkanoyloxy; carboxy,
Phenyl which may be substituted with one or more substituents selected from hydroxy, halogen, nitro, lower alkyl and lower alkoxy; phenoxy; cyclohexyl or formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula , Y is a group represented by the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ,F_0_～
_1 means the number of double bonds] Contains one or more of the compounds shown as active ingredients, or contains one or more of the compounds and ethephon as active ingredients. A plant growth regulator characterized by: (2) The active ingredient is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1_a means hydrogen or halogen, and R^2 means halogen or phenylthio, respectively). A plant growth regulator according to claim 1. (3) A patent in which the active ingredient is a compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein Z means hydrogen or phenyl which may be substituted with halogen or lower alkyl) The plant growth regulator according to claim 1.